Abstract
The Voronoi–Dirichlet polyhedra (VDP) and the method of intersecting spheres were used to perform a crystal-chemical analysis of all compounds studied to date whose structures contain rhodium atoms surrounded by oxygen atoms. All Rh atoms were found to have a coordination number (CN) equal to 6 and to form coordination polyhedra of two types, namely, the distorted octahedra RhO6 and RhO5Rh. A coordination number of 6 was found for all Rh(IV), Rh3.5+, and Rh(III) atoms, while a CN of 5+1 was found typical only of Rh2.5+ and Rh(II) atoms. The effect of the valence state of Rh on the main features of their crystal-chemical role in the structures is considered in terms of the 18-electron rule.
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